Process of producing aromatic alcohols and their derivatives.



. CHARLES METTLER OF MUNICH;y GERMANY i! "ai f i `P'RocfEss oiPRoDUciNGAROMATICALCQHOLSANDTHEIR D iR|vAT|i/5's.f

Beit known that LCHARLES MErTIiEn,

chemist, aciti'z'enof Switzerland, vof No.1?` Marsstra'ss'e, Munich,rinthe Kingdom' of. Ba-f f yVaria and Empire of Germany, hayeinyentedlcertain new and useful improvements in Proc-1 es seslfor the Productionof'Aromatic Alco-4 f hols` and their Derivativ lowing isaspecication. f

It has nothitherto been known that aire-7" duction ofY aromatic estersto f alcoholspforg ex- Y, `ample, vfromy ethyl-ester of benzoic' acidto`benzylaloohol t i (1,115*oooomflwni:CGHEomOH-Fcuon f has eyerbeenrealized.y i

I have new yfound i that i minnie sjeefs lhave'they 'roperty,'` underthefconditions suit-y able fort e saine, of taking upjhydrogen `andchanging into compounds comparatively poor in oxygen. y; Th1-'secourswhen arornaticesters g are reduced atinetal cathodes-'for i example,y

at lea'd `cathodeS- by means of yelectrolyti'c- .ally-separatedhydrogen. For thiS purpose it t cornes into consideration, concentratedSul-y furie acid which can be diluted with watera`l 1 o' i coholo racetic acid. In lieu'thereof an aque'- f alsobe carried out in'analkaline or neutral so@ i Intiem, in whichv case anf aqueous solution 7which contains the electrolyte s-rnixed withv the quantity of alcoholnec'eSSaryforthe soluv tion of the ester'.4 Ifone operates in yana'cidsol lution andreducesfplyway .of example ethyl after'afeufcient time.V lmy i is advantageous. to'v employ a dissolving agent for the ester,which iS at' the Sametime capable l Y of conducting theielect'riccurrent, as Such ous alcoholic .solutiony of hydrochloric acid can be'employed, andfinally such a reduction `can specification ofretten;"Patent l' L r i Application illallNmvitilier@@9044k SerialNoi-231,149. 'V

es,of which the fol@ a 1k w This courseof reactionsisgnotjonly vftheVariousethylestersofbenzoicacid;'1butiity t methyl estei' o1 aniscpaeid.'i

limited .150,

relates to. anew general class reaction of Varoi -In'atic`z-este1s.-`{It} isA particularly of value in that-it also holds'goodfor'substitutedaronatic esters. `Thus whenusin halo enfsub'stituted and I I ethylathen-.of meta-'- meta-bror'n'lben-y brom-be zoic acid.

1 Withregard tothe riroportionsi of :etherl andofalcoholthe`se ependuponl uite" af lI iurr'lberof'cir'cumstances.v Forexai'n'p e, con-yPatented l f formed out `'of',Inethylester of 'b enzoic acid,

' l oon I' iethyl ether otanisic alco- `h 225 f.

`diluted with water.

velectrolyti`c reduction of substances which stitution and temperatureplay an important part. If the methyl ester of benzoic acid is treated,the-production of alcohol .prevails formed, (two parts alcohol, one partether,) whereas out of ethyl ester of benzoic acid under analogousconditions more etheris formed (one part alcohol, two parts ether.) Theformation of ether is still more predominant in the case of thehalogen-substituted compounds. Thus, for example, the ethyl ester ofmeta-chlor-benzoic acid is exclusively reduced to ethyl ether ofmeta-chlor-benzyl alcohol. The reduction of the esters can also becarried out in an alkaline solution. As main products alcohols areobtained.

By means of suitable oxidizing agents the ethers, like the alcohols, caneasily be converted into aldehydes, and these form a suitable materialfor the dyeing industry for triplienyl-'methan dyestuffs and forartificial 1n 1go.

The following examples will now be given:

1. The cathode-space of an electrolyzing a paratus is charged with asolution having tlIie following composition: three hundred grams ofethyl ester of benzoic acid, three. hundred and iifty grams 'ofconcentrated sulfuric acid, five hundred grams of alcohol of ninety-sixper cent., one hundred grams of water. (In place of wateracorrespondinglydilute solution of sulfuric acid can of coursebeemployed.) The anode-space separated by an earthenware cell containssulfuric acid It is known that the are not readily and easily reducedcan be facilitated by employing for the cathode a metal having a highcathodic tension. Therefore the cathode of my apparatus consists of puresheet-lead, which is suitably prepared according to Tafels prescription,(Berichte der Deutschen Chem. Gesellschaft 332215,) and pure lead isemployed for the anode. A current of seven amperes per one hundredsquare centimeters cathode-surface is sent through the liquid; but thestreng-th of the current can be materially varied without disadvantage.By means of cooling the temperat-ure is kept between 20 and 30centigrade. `When no more hydrogen is absorbed,

`grams of alcohol.

the-cathode liquid is neutralized with about thirty per cent. soda-lye.Two layers are formed, of which the upper one consists of alcohol andthe products of reduction of the ethyl ester of benzoic acid. This isseparated distilled, and fractionized. The benzyl-ethyl ether boils at184, the benzyl alcohol at 205.

2. Under similar conditions as in Case 1 a cathode liquidy of thefollowing compositionnamely, one hundred and seventy grams of ethylester of meta-brom-benzoic acid, three hundred grams of concentratedsulfuric acid, five hundred grams of alcohol of ninety-six per centisreduced at a lead cathode with the aid of the electric current. Duringthe electrolysis the reaction product is se ara-ted for the greater arton the bottom of tiie cathodespace as oi It is drawn off and distilled.Between 235 to 239 the ethyl etherof metabrom-benzyl alcohol distils. At250 a small quantity of meta-brom-benzyl alcohol passes over.

3. In the cathode-space of an electrolyzing apparatus a solution asfollows is laced: one hundred grams ofethyl ester of enzoic acid, sixhundred grams of thirty-per-cent. aqueous sal-ammoniac solution, sixhundred The anode-space separated by an earthenware cell contains dilutesulfuric acid or ammonium-sulfate solution. Cathode and anode consist ofurelead. Electrolysis proceeds while the iquid is cooled, the currenthaving a strength of six amperes per one hundred square centimeterscathodesurface. When no more. hydrogen is absorbed, the alcohol isdistilled off and the liquid is acidulated. Benzyl alcohol separates forthe most part. It is removed and disuned. (195%0 205.)

What I claim is- Process for the roduction of aromatic alcohols andtheir et ers, which consists in exposing the aromatic esters in adissolving agent, capable of conducting the electric current in thecathode-space of an electrolytic apparatus in using for the cathode amaterial of a specially-high cathodic tension, then neutralizing thecathode liquid, then se arating the reaction product and finallydistilling, substantially as described.

In witness whereof I have hereunto set my hand in the presence of twowitnesses.

CHARLES METTLER.

Witnesses:

ULYssEs J. BYWATER, ABRAHAM ScHLEsiNGER.

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